臺灣博碩士論文加值系統

隨著科技快速進步，使得全球對環境與能源日益重視，依賴程度也與日俱增；然而我們所生活的社會正面臨著污染、化石燃料不足、全球暖化等環境與能源危機。為了克服這些問題，迫切需要清潔和可再生能源材料及其裝置。超級電容器不僅擁有優異的功率密度與儲電能力，其亦能提供高速充放電速率及長的循環壽命，且操作安全、具環境友好性，其中微型超級電容器由於可進一步與MEMS和CMOS集成，近年來引起了廣泛的研究興趣。
本研究以濺鍍之MoOx薄膜為活性物質製備指叉式微型固態超級電容器，探討具有不同指叉結構組態(指叉總數、間隙、寬度及長度)的平面微型超級電容器，其幾何構型對電化學性質的影響。此外，本研究引入了基於MoOx/Ag多層薄膜結構之指叉式微型固態超級電容器的新概念。電化學交流阻抗分析證實了由於銀薄膜的摻入，MoOx金屬氧化物之低導電率的缺陷得到有效的改善，使得其體積比電容與能量和功率密度遠高於基於MoOx單層薄膜結構的指叉式微型固態超級電容器，且其體積比電容隨著銀摻入的量增而逐漸增加；但加入過量的銀，比電容在連續充放電後的保持率並不會隨此增加，每層銀厚度為1.5 nm的MoOx/Ag多層薄膜結構經過10000次之大數量的循環次數之後，表現出最優異的循環穩定性和最高的體積比電容。
活性材料的高導電性對基於金屬氧化物的擬電容實現高的比電容以及功率和能量密度至關重要。本研究基於單層MoOx與多層MoOx/Ag薄膜結構之指叉式微型固態超級電容器皆展現相當優異的電化學性能，其結果表明所使用之方法和設計對微型儲能系統的應用表現出巨大的前景。

With the scientific and technological advancements, the society which we live is facing the energy and environmental related problems such as pollution, deficiency of fossil fuels, and global warming. In order to resolve these issues, green-energy and renewable materials as well as their devices are demanded. Supercapacitors (SCs) exhibit high specific capacitance and power density, fast charge-discharge rate, and long cycle life. In addition, they are safe in operation and environmental friendly. Recently, micro-supercapacitors (MSCs) have attracted much interests since they can be further integrated into MEMS and CMOS.
In this work, we introduce planar interdigitated electrode structure based on MoOx thin film electrode materials, which can be further fabricated to on-chip and all-solid-state MSC. This study investigated the influence of the geometric configuration of planar interdigitated MSCs with different interdigitated patterns (varying the interspace, width, length and number of interdigitated fingers) on their electrochemical properties. Furthermore, we introduce a new concept to fabricate MSC based on MoOx/Ag multilayers, with which the volumetric capacitance is much higher than that of the bare MoOx-based MSC. MoOx/Ag multilayer MSC also demonstrates higher energy density and power density. Electrochemical impedance spectroscopy (EIS) confirmed that the electrical conductivity of MoOx was significantly improved due to the incorporation of silver. The corresponding volumetric capacitance increases as the the silver thickness increases. But with the excess silver, the capacitance retention rate was found to be degraded. MoOx/Ag multilayers MSC with a thickness of 1.5 nm for each Ag layer exhibits most excellent cycle stability and highest volumetric capacitance after a large cycling number of 10000 times.
This work indicates that high electronic conductivity of the electrode material is crucial to achieving high specific capacity as well as power and energy density for pseudocapacitors. These excellent electrochemical performance of results suggest that our method and design show great promise for applications in integrated energy storage for all solid-state microsystems technologies.

摘要 I
Abstract II
致謝 IV
目錄 VI
圖目錄 X
表目錄 XIV
第一章 緒論 1
1.1 前言 1
1.2 基本原理與文獻回顧 3
1.2.1 超級電容器簡介 3
1.2.2 超級電容器之儲能機制 4
1.2.2.1 電雙層電容器 4
1.2.2.2 擬電容器 7
1.2.2.3 混合電容器 8
1.2.3 超級電容器之電極材料 9
1.2.3.1 碳系材料 9
1.2.3.2 金屬氧化物 10
1.2.3.3 導電高分子 11
1.2.4 超級電容器之電解質 12
1.2.5 超級電容器之電化學原理與技術 14
1.2.5.1 循環伏安法 14
1.2.5.2 恆電流充放電法 16
1.2.5.3 電化學交流阻抗分析 17
1.2.6 微型超級電容器 18
1.3 研究動機與目的 21
第二章 實驗程序與方法 23
2.1 實驗藥品 23
2.2 製程與分析儀器 24
2.2.1 雷射光罩製作系統(Laser Direct Write Image System) 24
2.2.2 光罩對準曝光機(Mask Aligner) 24
2.2.3 旋轉塗佈機(Spin Coater) 24
2.2.4 電漿輔助化學氣相沉積系統(Plasma Enhanced Chemical Vapor Deposition, PECVD) 25
2.2.5 高真空電子束暨熱阻式蒸鍍系統(E-gun & Thermal Evaporation System) 25
2.2.6 射頻與直流磁控濺鍍機(RF&DC Magnetron Sputtering) 26
2.2.7 紫外光臭氧清洗機(UV-Ozone Stripper) 26
2.2.8 恆電位儀(Potentiostat) 27
2.2.9 X射線光電子能譜(X-Ray Photoelectron spectroscopy, XPS) 27
2.2.10 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 28
2.2.11 掃描穿透式電子顯微鏡(Scanning Transmission Electron Microscopy, STEM) 28
2.2.12 雙束型聚焦離子束顯微鏡(Dual Beam Focus Ion Beam, DB-FIB) 29
2.2.13 原子力顯微鏡(Atomic Force Microscope, AFM) 29
2.3 實驗流程 30
2.4 實驗製程 31
2.4.1 指叉圖形結構與組態之設計 31
2.4.2 製備SiO2/Si基板 33
2.4.3 黃光微影 33
2.4.4 製備集電極 33
2.4.5 製備活性物質 34
2.4.6 掀離製程 35
2.4.7 製備固態電解質 35
2.4.8 製備指叉式微型固態超級電容器 35
第三章 實驗結果與討論 37
3.1 材料分析 37
3.1.1穿透式電子顯微鏡分析(TEM) 37
3.1.2掃描電子顯微鏡分析(SEM) 42
3.1.3 原子力顯微鏡分析(AFM) 42
3.1.4 X射線光電子能譜分析(XPS) 45
3.2 不同結構組態之MoOx指叉式微型固態超級電容器特性分析 47
3.2.1 循環伏安與恆電流充放電分析 47
3.2.2 電化學交流阻抗分析 52
3.3 MoOx與MoOx/Ag指叉式微型固態超級電容器特性分析 55
3.3.1 循環伏安與恆電流充放電分析 55
3.2.2 電化學交流阻抗分析 60
3.2.3 循環穩定性分析 61
3.2.4 頻率響應分析 64
第四章 結論 67
第五章 參考文獻 69

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